Successfully complete Story mode with two different characters to unlock Ace.
Play as BlackbeardSuccessfully complete Story mode with Shanks to unlock Blackbeard.
Play as CrocodileSuccessfully complete Story mode with three different characters to unlock Crocodile.
Play as EnerSuccessfully complete Story mode with five different characters to unlock Ener.
Play as MihawkSuccessfully complete Story mode with all other characters to unlock Mihawk.
Play as ShanksSuccessfully complete Story mode with Mihawk to unlock Shanks.
Play as SmokerSuccessfully complete Story mode to unlock Smoker.
Play as ViviSuccessfully complete Story mode with four different characters to unlock Vivi.